US6872840B1 - Synthesis of 8-membered carbocyclic compound having diexomethylene groups - Google Patents
Synthesis of 8-membered carbocyclic compound having diexomethylene groups Download PDFInfo
- Publication number
- US6872840B1 US6872840B1 US10/823,708 US82370804A US6872840B1 US 6872840 B1 US6872840 B1 US 6872840B1 US 82370804 A US82370804 A US 82370804A US 6872840 B1 US6872840 B1 US 6872840B1
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- US
- United States
- Prior art keywords
- compound
- membered carbocyclic
- reaction
- membered
- carbocyclic compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 0 [1*]C12OC(CC(=C)C1=C)CC([3*])C2[2*] Chemical compound [1*]C12OC(CC(=C)C1=C)CC([3*])C2[2*] 0.000 description 6
- CCPBYKLPXGZVSL-UHFFFAOYSA-N C=C1CC2CC3=CC=CC=C3C(O2)C1=C.C=C=C(CC1CC2=CC=CC=C2C(O)O1)C[Si](C)(C)C Chemical compound C=C1CC2CC3=CC=CC=C3C(O2)C1=C.C=C=C(CC1CC2=CC=CC=C2C(O)O1)C[Si](C)(C)C CCPBYKLPXGZVSL-UHFFFAOYSA-N 0.000 description 1
- DJNVANPREYPRNZ-UHFFFAOYSA-N C=C1CC2CC3=CC=CC=C3C(O2)C1=C.COC(=O)C#CC(=O)OC.COC(=O)C1=C(C(=O)OC)CC2=C(C1)CC1CC3=CC=CC=C3C2O1 Chemical compound C=C1CC2CC3=CC=CC=C3C(O2)C1=C.COC(=O)C#CC(=O)OC.COC(=O)C1=C(C(=O)OC)CC2=C(C1)CC1CC3=CC=CC=C3C2O1 DJNVANPREYPRNZ-UHFFFAOYSA-N 0.000 description 1
- XZZGTDLJUOPWCZ-UHFFFAOYSA-N C=C1CC2CCC3CCCC3(O2)C1=C.C=C=C(CC(O)CCC1CCCC1=O)C[Si](C)(C)C Chemical compound C=C1CC2CCC3CCCC3(O2)C1=C.C=C=C(CC(O)CCC1CCCC1=O)C[Si](C)(C)C XZZGTDLJUOPWCZ-UHFFFAOYSA-N 0.000 description 1
- CQEONXWJQIMRDG-UHFFFAOYSA-N C=C1CC2CCCC(C3=CC=CC=C3)(O2)C1=C.C=C=C(CC(O)CCCC(=O)C1=CC=CC=C1)C[Si](C)(C)C Chemical compound C=C1CC2CCCC(C3=CC=CC=C3)(O2)C1=C.C=C=C(CC(O)CCCC(=O)C1=CC=CC=C1)C[Si](C)(C)C CQEONXWJQIMRDG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/08—Bridged systems
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
- A61K31/34—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having five-membered rings with one oxygen as the only ring hetero atom, e.g. isosorbide
- A61K31/343—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having five-membered rings with one oxygen as the only ring hetero atom, e.g. isosorbide condensed with a carbocyclic ring, e.g. coumaran, bufuralol, befunolol, clobenfurol, amiodarone
Definitions
- the present invention relates to a synthesis of an 8-membered carbocyclic compound having diexomethylene groups, more particularly to a synthesis of an 8-membered carbocyclic compound having diexomethylene groups, a novel compound having the structure represented by the following Chemical Formula 1, from trimethylsilanylmethyl-allenol derivative by the intramolecular Prins cyclization using Lewis acid.
- the 8-membered carbocyclic compound is a useful intermediate for synthesis of other multicarbocyclic compounds.
- R 1 is a phenyl group
- R 2 and R 3 is respectively a hydrogen atom, or R 1 , R 2 and R 3 may be connected with neighboring substituents to form a 5 to 10-membered aliphatic or aromatic ring.
- 8-membered carbocyclic compounds are important ingredients of biologically active natural substances and medicines. Recently, they are gaining interest in genetics because they are known to take part in cell division. For example, Taxol, which is widely known as anticancer drug [Taxane Anticancer Agents, ACS Symposium Series 583], has an 8-membered ring. Besides, since 8-membered carbocyclic compounds have good biological activities, development of an 8-membered carbocyclic compound with a new structure is a prerequisite for drug researches.
- a carbocyclic compound having diexomethylene groups can be expanded to other multicarbocyclic compounds through Diels-Alder reactions. Therefore, the compound represented by Chemical Formula 1, which has diexomethylene groups, is a very useful intermediate in synthesizing a multicarbocyclic compound via Diels-Alder reactions.
- the present invention is characterized by an 8-membered carbocyclic compound having a new structure, which is represented by the following Chemical Formula 1:
- R 1 is a phenyl group
- R 2 and R 3 is respectively a hydrogen atom, or R 1 , R 2 and R 3 may be connected with neighboring substituents to form a 5 to 10-membered aliphatic or aromatic ring.
- the present invention is characterized by a method of synthesizing the compound represented by Chemical Formula 1 from a trimethylsilanylmethyl-allenol derivative by the intramolecular Prins cyclization in the presence of Lewis acid.
- the 8-membered carbocyclic compound represented by Chemical Formula 1, which is provided by the present invention, is a novel compound having diexomethylene groups, and it can be used as an active ingredient of medicines, or intermediate of synthesizing multicarbocyclic compounds in the field of medicine and precise chemistry.
- the present invention also provides a method of synthesizing the compound represented by Chemical Formula 1 from a trimethylsilanylmethyl-allenol derivative by the intramolecular Prins cyclization in the presence of Lewis acid.
- TMSOTf trimethylsilyl trifluoromethanesulfonate
- the Lewis acid is used in 1.0 to 1.5 equivalent of the starting material, trimethylsilanylmethyl-allenol derivative.
- reaction solvent common organic solvents such as diethyl ether, tetrahydrofuran, dichloromethane, chloroform and ethyl acetate can be used. Most preferably, diethyl ether is used. The reaction was performed at from ⁇ 90° C. to room temperature (25° C.) for
- the compound represented by Chemical Formula 1 is useful in the field of medicine and precise chemistry. Because the compound represented by Chemical Formula 1 has diexomethylene groups, other multicarbocyclic compounds can be prepared from it via Diels-Alder reactions.
- the present invention offers the following advantages:
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Medicinal Chemistry (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020030064384A KR100558849B1 (ko) | 2003-09-17 | 2003-09-17 | 두 개의 엑소 메틸렌을 가지는 8각형 고리화합물과 이의제조방법 |
| KR10-2003-0064384 | 2003-09-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| US20050059732A1 US20050059732A1 (en) | 2005-03-17 |
| US6872840B1 true US6872840B1 (en) | 2005-03-29 |
Family
ID=34270742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US10/823,708 Expired - Fee Related US6872840B1 (en) | 2003-09-17 | 2004-04-14 | Synthesis of 8-membered carbocyclic compound having diexomethylene groups |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US6872840B1 (ko) |
| JP (1) | JP2005089429A (ko) |
| KR (1) | KR100558849B1 (ko) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100645373B1 (ko) * | 2005-07-08 | 2006-11-14 | 한국과학기술연구원 | 세 고리형 테트라하이드로퓨란 락톤 화합물과 이의 제조방법 |
| KR100645372B1 (ko) * | 2005-07-08 | 2006-11-14 | 한국과학기술연구원 | 두 고리형 테트라하이드로퓨란 락톤 화합물과 이의 제조방법 |
| KR100645371B1 (ko) * | 2005-07-08 | 2006-11-14 | 한국과학기술연구원 | 두 고리형 테트라하이드로퓨란 화합물과 이의 제조방법 |
-
2003
- 2003-09-17 KR KR1020030064384A patent/KR100558849B1/ko not_active IP Right Cessation
- 2003-10-17 JP JP2003358545A patent/JP2005089429A/ja active Pending
-
2004
- 2004-04-14 US US10/823,708 patent/US6872840B1/en not_active Expired - Fee Related
Non-Patent Citations (3)
| Title |
|---|
| Article "The 91<st >National Meeting of the Korean Chemical Society", ISSN 1229-6708, Apr. 18-19, 2003, p. 363. |
| Paul A. Wender, et al., "Transition Metal-Catalyzed [6+2] Cycloadditions of 2-Vinylcyclobutanones and Alkenes: A New Reaction for the Synthesis of Eight-Membered Rings", J. Am. Chem. Soc., vol. 122, No. 32, 2000 American Chemical Society, pp. 7815-7816. |
| Scott R. Gilbertson, et al., "Rhodium Catalyzed [4+2+2] Cycloaddition and Alkyne Insertion: A New Route to Eight-Membered Rings", J. Am. Chem. Soc., vol. 124, No. 30, 2002, American Chemical Society, pp. 8784-8785. |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100558849B1 (ko) | 2006-03-10 |
| US20050059732A1 (en) | 2005-03-17 |
| JP2005089429A (ja) | 2005-04-07 |
| KR20050028095A (ko) | 2005-03-22 |
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